CN113299937A - Method for recycling waste zinc-manganese dry batteries and directly using waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries - Google Patents
Method for recycling waste zinc-manganese dry batteries and directly using waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries Download PDFInfo
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Abstract
The invention discloses a method for recycling waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries, which belongs to the technical field of waste resource comprehensive utilization and secondary batteries, and mainly comprises the following steps: step 1: pretreating the waste zinc-manganese dry battery solid to obtain a waste zinc-manganese dry battery suspension; step 2: and (3) sequentially carrying out primary filtration, heating concentration, primary pH adjustment, secondary filtration and secondary pH adjustment on the waste zinc-manganese dry battery suspension obtained in the step (1) to prepare the electrolyte solution which can be directly used for the rechargeable zinc-manganese battery. The invention provides a method for recycling waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries for the first time, and can effectively solve the problems of high energy consumption, complex process and high cost in the conventional zinc-manganese dry battery recycling method.
Description
Technical Field
The invention relates to the technical field of comprehensive utilization of waste resources and secondary batteries, in particular to a method for recycling waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries in rechargeable zinc-manganese batteries.
Background
Zn-MnO 2 Galvanic cells (ZMPBs) are a mature technology that is widely used in small electronic devices, electronic toys, and portable electronic devices. ZMPB made of manganese dioxide (MnO) 2 ) As positive electrode, zinc (Zn) as negative electrode, potassium hydroxide (basic ZMPB is KOH) or ammonium chloride (neutral ZMPB is NH) 4 Cl) aqueous solution is composed of electrolyte and a small amount of conductive corrosion inhibition additive. During discharge, the cathode Zn is oxidized, and the anode MnO is 2 Is reduced; thereby providing a stable discharge current in the external circuit. Due to the advantages of low cost and simple production process, ZMPB occupies over 75 percent of the portable battery market. However, the recycling of the corresponding waste zinc-manganese dry batteries has not been solved on an industrial scale.
The existing recovery methods for the zinc-manganese dry battery comprise a dry method, a wet method and a dry-wet mixing method. Among them, the dry method mainly uses high temperature to oxidize, reduce, decompose, volatilize and condense the metal and compound in the waste dry battery for recovery, but the disadvantages are large energy consumption and high equipment cost. The wet process is based on the property that metal and its compound in waste dry battery are easily dissolved in acid, and the solution is first dissolved to obtain solution, and then the solution is used to produce zinc sulfate, manganese sulfate and other chemical by-products or purified and passed through electrode to produce Zn and MnO 2 And the like, but has the disadvantages of more added chemical substances, low product purity, long process flow and easy generation of secondary pollution. The dry-wet mixing method is realized by combining a dry method and a wet method, but is also seriously troubled by the problems of high energy consumption, long flow path and the like. The fundamental reason of the existing zinc-manganese dry battery recovery method is that the waste battery is completely recovered to the initial state, but the processes for impurity separation and zinc-manganese separate recovery in the process mainly cause high energy consumption, long process and large investmentThe important factor. Therefore, it is very significant to provide a method for recycling waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries in rechargeable zinc-manganese batteries.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a method for recycling waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries for the first time, and can effectively solve the problems of high energy consumption, complex process and high cost in the conventional zinc-manganese dry battery recycling method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for recycling waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries, which specifically comprises the following steps:
step 1: pretreating the waste zinc-manganese dry battery solid to obtain a waste zinc-manganese dry battery suspension;
step 2: and (3) sequentially carrying out primary filtration, heating concentration, primary pH adjustment, secondary filtration and secondary pH adjustment on the waste zinc-manganese dry battery suspension obtained in the step (1) to prepare the electrolyte solution which can be directly used for the rechargeable zinc-manganese battery.
The invention provides a method for recycling waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries for the first time, which comprises the steps of pretreating solid waste zinc-manganese dry batteries to obtain suspension of the waste zinc-manganese dry batteries, filtering the suspension of the waste zinc-manganese dry batteries for the first time to remove insoluble solid impurities to obtain transparent and clear solution, heating and concentrating the solution to remove excessive hydrogen peroxide in the solution, and regulating the pH value for the first time to ensure that Fe is directly used for the rechargeable zinc-manganese batteries 3+ Precipitating in the form of precipitate, filtering to remove, and adjusting pH to obtain ZnSO-containing solution 4 -MnSO 4 The electrolyte solution of the system can be directly used for the rechargeable zinc-manganese battery, so that the rechargeable zinc-manganese battery has excellent electrical properties.
Further, the pretreatment process in the step 1 specifically comprises:
step 1.1: firstly, breaking and dismantling alkaline waste zinc-manganese dry batteries and collecting all substances at positive and negative electrodes;
or firstly breaking and dismantling the neutral waste zinc-manganese dry battery, calcining and collecting all substances at the positive and negative electrodes;
step 1.2: and (2) dissolving the substance collected in the step (1.1) in a sulfuric acid-hydrogen peroxide solution to obtain the suspension of the waste zinc-manganese dry battery.
The method comprises the steps of firstly classifying the waste zinc-manganese batteries into alkaline waste zinc-manganese dry batteries and neutral carbon waste zinc-manganese dry batteries according to different electrolytes of the waste zinc-manganese dry batteries, and preprocessing the waste zinc-manganese dry batteries. Breaking and dissolving alkaline waste zinc-manganese dry batteries to obtain a waste zinc-manganese dry battery suspension containing active substances at positive and negative electrodes; the neutral carbon waste zinc-manganese dry battery is broken and dismantled and then calcined in the air, ammonium chloride and starch in the neutral carbon waste zinc-manganese dry battery can be decomposed and oxidized to be removed, and then sulfuric acid-hydrogen peroxide solution is added for dissolving to obtain waste zinc-manganese dry battery suspension containing active substances at positive and negative electrodes.
Further, the temperature of calcination in step 1.1 is 400-500 ℃, preferably 450 ℃; the duration is 1 to 2 hours, preferably 1 hour.
Furthermore, in step 1.2, the molar concentrations of the sulfuric acid and the hydrogen peroxide in the sulfuric acid-hydrogen peroxide solution are both 1 to 2mol/L, and preferably 1mol/L.
Further, the pH value is adjusted to 3-5, preferably 3.2 for the first time in the step 2; the second pH is adjusted to 1.5 to 2.5, preferably to 1.9.
In the invention, the pH is adjusted by adding an alkaline solution, which is not specially limited and can be potassium hydroxide solution, sodium carbonate solution, potassium carbonate solution and the like, and the pH is adjusted to the required range.
Further, the heating concentration temperature in the step 2 is 70-90 ℃, and preferably 80 ℃; the duration is 5 to 7 hours, preferably 6 hours.
Furthermore, the method for recycling the waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries for the rechargeable zinc-manganese batteries also comprises the step of assembling the electrolyte solution obtained in the step 2 as the working solution of the rechargeable zinc-manganese batteries with the assistance of positive and negative electrodes.
The rechargeable zinc-manganese battery and the assembly method thereof are not specially limited, and the simplest graphite rod can be directly used as a positive electrode and a negative electrode, and an electrolyte solution obtained by recovering waste zinc-manganese dry batteries is added to be used as a working solution of the rechargeable zinc-manganese battery to form the simple rechargeable zinc-manganese battery; the rechargeable zinc-manganese battery can also be prepared by adding a small amount of Pt and other metal modified electrode materials into the existing electrode, adding other electrochemically acceptable reagents and adopting a conventional method.
The invention has the following advantages:
1. the invention provides a method for recovering waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries in rechargeable zinc-manganese batteries for the first time. The leachate is simply purified and directly used as working solution to prepare the electrolytic rechargeable zinc-manganese battery. The experimental result shows that the neutral waste Zn-MnO is 2 The performance of the recovery liquid of the primary battery is superior to that of alkaline waste Zn-MnO 2 The primary battery is superior to the solution prepared by chemical pure reagent. The electrolyte solution obtained by recycling the waste zinc-manganese dry batteries is directly used as the working solution of the rechargeable zinc-manganese battery, and the positive and negative electrodes are assisted, so that the simplest rechargeable zinc-manganese battery assembled by the rechargeable zinc-manganese battery also has high coulombic efficiency, high energy density and long cycle life, and has good application potential;
2. the method provided by the invention has the advantages that the waste zinc-manganese dry batteries are recycled through a simple hydrometallurgical process and directly used for rechargeable zinc-manganese dry batteries for the first time, a new method is provided for recycling and energy storage of ZMPB, and the problems of high energy consumption, complex process and high cost in the conventional zinc-manganese dry battery recycling method can be effectively solved.
Drawings
FIG. 1 is a schematic view of the process of the present invention;
FIG. 2 is a structural diagram of a simple rechargeable zinc-manganese battery of the present invention;
FIG. 3 is a diagram showing the results of testing the charging and discharging performance of the rechargeable zinc-manganese dioxide battery under working solutions with different pH values;
FIG. 4 is a diagram showing the results of testing the performance of the rechargeable zinc-manganese dioxide battery of the present invention under different charging currents;
FIG. 5 is a diagram showing the results of cycle performance tests of the rechargeable zinc-manganese dioxide battery of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising a," "8230," "8230," or "comprising" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a method for recycling waste zinc-manganese dry batteries (specifically neutral zinc-manganese dry batteries) and directly using the waste zinc-manganese dry batteries in rechargeable zinc-manganese batteries, which specifically comprises the following steps:
step 1: firstly, removing the battery outer package and the anode carbon rod of the neutral waste zinc-manganese dry battery, then directly calcining for 1 hour at 450 ℃ in the air, and decomposing and oxidizing ammonium chloride and starch in the battery outer package and the anode carbon rod; collecting all the calcined substances into a beaker, adding 1mol/L sulfuric acid-hydrogen peroxide solution into the beaker, and fully stirring and dissolving to obtain a waste zinc-manganese dry battery suspension;
and 2, step: filtering the waste zinc-manganese dry battery suspension obtained in the step 1 to obtain a clear and transparent solution; then heating the clear and transparent solution at 80 ℃ for 6 hours to obtain a concentrated solution; the pH of the resulting concentrated solution was adjusted to 3.2 with 0.1M potassium hydroxide solution and filtered again to remove Fe 3+ And adjusting the pH of the obtained concentrated solution to 1.95 by using 0.1M potassium hydroxide solution again to obtain an electrolyte solution which can be directly used for the rechargeable zinc-manganese battery.
Example 2
The present example provides a method for recycling waste zinc-manganese dry batteries (specifically, neutral zinc-manganese dry batteries) and directly using the waste zinc-manganese dry batteries as rechargeable zinc-manganese batteries, which only differs from example 1 in that: in step 2, the pH is adjusted to 1.64 for the second time, and the rest steps and parameters are the same.
Example 3
This example provides a method for recycling waste zinc-manganese dry batteries (specifically, neutral zinc-manganese dry batteries) and directly using the recycled waste zinc-manganese dry batteries in rechargeable zinc-manganese batteries, which differs from example 1 only in that: in step 2, the pH is adjusted to 1.73 for the second time, and the rest steps and parameters are the same.
Example 4
This example provides a method for recycling waste zinc-manganese dry batteries (specifically, neutral zinc-manganese dry batteries) and directly using the recycled waste zinc-manganese dry batteries in rechargeable zinc-manganese batteries, which differs from example 1 only in that: in step 2, the pH is adjusted to 1.86 for the second time, and the rest steps and parameters are the same.
Example 5
This example provides a method for recycling waste zinc-manganese dry batteries (specifically, neutral zinc-manganese dry batteries) and directly using the recycled waste zinc-manganese dry batteries in rechargeable zinc-manganese batteries, which differs from example 1 only in that: in step 2, the pH is adjusted to 2.14 for the second time, and the rest steps and parameters are the same.
Example 6
The embodiment provides a method for recycling waste zinc-manganese dry batteries (specifically alkaline waste zinc-manganese dry batteries) and directly using the waste zinc-manganese dry batteries in rechargeable zinc-manganese batteries, which specifically comprises the following steps:
step 1: firstly, removing an outer battery package and a positive carbon rod of an alkaline waste zinc-manganese dry battery, collecting all substances at a positive electrode and a negative electrode into a beaker, adding 1mol/L sulfuric acid-hydrogen peroxide solution into the beaker, and fully stirring and dissolving to obtain a suspension of the waste zinc-manganese dry battery;
step 2: filtering the waste zinc-manganese dry battery suspension obtained in the step 1 to obtain a clear and transparent solution; then heating the clear and transparent solution at 80 ℃ for 6 hours to obtain a concentrated solution; the pH of the resulting concentrated solution was adjusted to 3.2 with 0.1M potassium hydroxide solution and filtered again to remove Fe 3+ Impurities, and the pH of the resulting concentrated solution was again adjusted to 1.92 with 0.1M potassium hydroxide solution to give an electrolyte solution that could be used directly in rechargeable zinc-manganese batteries.
Example 7
The embodiment provides a method for recycling waste zinc-manganese dry batteries (specifically alkaline waste zinc-manganese dry batteries) and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries, and the method is different from the embodiment 6 only in that: in step 2, the pH is adjusted to 1.78 for the second time, and the rest steps and parameters are the same.
Example 8
The present example provides a method for recycling waste zinc-manganese dry batteries (specifically, alkaline waste zinc-manganese dry batteries) and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries, which is different from example 6 only in that: in step 2, the pH is adjusted to 1.87 for the second time, and the rest steps and parameters are the same.
Example 9
The embodiment provides a method for recycling waste zinc-manganese dry batteries (specifically alkaline waste zinc-manganese dry batteries) and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries, and the method is different from the embodiment 6 only in that: in step 2, the pH is adjusted to 2.12 for the second time, and the rest steps and parameters are the same.
Example 10
The present example provides a method for recycling waste zinc-manganese dry batteries (specifically, alkaline waste zinc-manganese dry batteries) and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries, which is different from example 6 only in that: in step 2, the pH is adjusted to 2.38 for the second time, and the rest steps and parameters are the same.
Examples of the experiments
First, the electrolyte solutions obtained in examples 1 and 6 were characterized by an inductively coupled plasma emission spectrometer (ICP-OES) in this experimental example, and the elemental compositions and concentrations thereof were measured as shown in tables 1 and 2. The ICP-OES results show that the predominant metal ions in both neutral and basic ZMPB recovery solutions are Zn 2+ And Mn 2+ . For neutral ZMPB: k + And Na + KOH from use in pH adjustment neutralization; and for basic ZMPB: k is + And Na + From the neutralizing agent KOH and the cell electrolyte itself.
TABLE 1 elemental composition and concentration of recovered solution of neutral waste zinc-manganese dioxide dry cell
TABLE 2 elemental composition and concentration of alkaline waste zinc-manganese dioxide dry cell recycling solution
In order to eliminate the effect of different concentrations on the cell performance, the concentrations of the main ions in the electrolyte solutions obtained in examples 1 to 10 were passed through deionized water and an analytical reagent (ZnSO) in this experimental example 4 ·H 2 O,MnSO 4 ·H 2 O,K 2 SO 4 And Na 2 SO 4 ) Concentration normalization treatment was performed to obtain Zn in the electrolyte solutions of examples 1 to 10 2+ /Mn 2+ The concentrations are all 1M, K + The concentration is 0.4M + The concentrations were all 0.05M. At the same time, a reference solution was prepared with deionized water and the same concentration of analytical reagent. After adjusting the ion concentration, the electrolyte solution and the reference solution obtained in examples 1 to 10 were used as working solutions and added to a home-made RZMB (rechargeable zinc-manganese battery), and the simple RZMB was as shown in FIG. 2. The RZMB comprises 30 ml of working solution and two graphite rods which are respectively used as a positive electrode and a negative electrode, and the active geometric area on the graphite rods is 3.5cm- 2 . According to different working solutions, the batteries are named as RZMB-N (taking the electrolyte solution obtained by recycling neutral waste zinc-manganese dry batteries as the working solution), RZMB-A (taking the electrolyte solution obtained by recycling alkaline waste zinc-manganese dry batteries as the working solution) and RZMB-B (taking ase:Sub>A reference solution as the working solution).
The RZMB-N, RZMB-A and RZMB-B batteries were first subjected to constant voltage charge-constant current discharge tests. The constant voltage charging process was performed at 2.2V, and the charging capacity was set to 3.5C (12.6 mAh). The constant current discharge process was carried out at 7.5mA with the terminal discharge voltage set to 0.8V. The charge and discharge properties of the batteries of working solutions of different pH values obtained in examples 1 to 10 were tested, and the test results are shown in fig. 3. The results show that: the change trends of the three types of the RZMB-N, the RZMB-N and the RZMB-A batteries are the same, the coulombic efficiency is gradually reduced along with the gradual reduction of the pH, and the energy efficiency is firstly increased and then reduced; the energy efficiency was highest at pH 1.95 (example 1) and 1.92 (example 6), respectively 61.54% and 52.58%, and the coulombic efficiency was highest, respectively 87.57% and 67.42%. Thus, the optimal working pH for the electrolytic RZMB of the present invention is 1.9. In the optimal pH range, the coulombic efficiency and the energy efficiency of the RZMB-N are higher than those of the RZMB-B and the RZMB-A.
This experimental example based on the above experimental results, the electrolyte solution obtained in example 1 was used as a working solution, and the battery performance at various charging currents at a stirring speed of 100rpm was tested, as shown in fig. 4. The experimental results show that Mn 2+ 、Zn 2+ 、H + The charging voltage of the battery is obviously lower than 2.2V due to the addition of the plasma and the stirring and conveying, and the discharging voltage platform is improved to-1.7V. Meanwhile, when the current is 7.5, 8.0, 8.5 and 9.0mA, the energy efficiency of RZMB-N is 61.92%, 69.81%, 71.11% and 72.33%, respectively, and the coulombic efficiency is 78.39%, 86.23%, 88.38% and 90.17%, respectively. However, when the charging current was further increased to 9.5mA, the battery discharge process did not improve significantly. More energy is consumed during the charging process due to the increase of the polarization of the battery, so that the energy efficiency of the battery slightly drops to 71.52%, and the coulomb efficiency remains unchanged (90.32%).
In this experimental example, the electrolyte solution obtained in example 1 was used as a working solution, and the cycle performance was measured at a charge current of 9.0mA, a discharge current of 7.5mA, and a fixed charge capacity of 3.5C (12.6 mAh), and the results are shown in fig. 5. The results show that the coulombic efficiency of the RZMB-N drops from 90.16% to 90.09% and the energy efficiency rises from 72.16% to 76.53% in 500 cycles. The results show that RZMB-N prepared from neutral ZMPB has excellent cycling stability.
In summary, the whole process flow chart is shown in fig. 1 by recycling and directly converting the waste zinc-manganese dry batteries into the rechargeable zinc-manganese batteries, and the obtained rechargeable zinc-manganese batteries have high coulomb efficiency, high energy density and long cycle life. Due to the characteristics, the electrolytic RZMB has wide application prospect in large-scale energy storage devices such as wind power generation auxiliary adjustment devices, so that the pollution to the environment is avoided, and the acquisition and application of renewable energy sources are increased.
The foregoing is merely exemplary and illustrative of the present invention and it is within the purview of one skilled in the art to modify or supplement the embodiments described or to substitute similar ones without the exercise of inventive faculty, and still fall within the scope of the claims.
Claims (7)
1. A method for recycling waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries is characterized by comprising the following steps:
step 1: pretreating the waste zinc-manganese dry battery solid to obtain a waste zinc-manganese dry battery suspension;
step 2: and (2) sequentially carrying out primary filtration, heating concentration, primary pH adjustment, secondary filtration and secondary pH adjustment on the suspension liquid of the waste zinc-manganese dry batteries obtained in the step (1) to prepare an electrolyte solution which can be directly used for rechargeable zinc-manganese batteries.
2. The method for recycling waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries according to claim 1, wherein the pretreatment process in the step 1 is specifically as follows:
step 1.1: firstly, breaking and dismantling alkaline waste zinc-manganese dry batteries and collecting all substances at positive and negative electrodes;
or firstly breaking and dismantling the neutral waste zinc-manganese dry battery, calcining and collecting all substances at the positive and negative electrodes;
step 1.2: and (3) dissolving the substance collected in the step (1.1) in a sulfuric acid-hydrogen peroxide solution to obtain the suspension of the waste zinc-manganese dry battery.
3. The method for recycling and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries according to claim 2, wherein the calcination in the step 1.1 is carried out at a temperature of 400-500 ℃ for a period of 1-2 hours.
4. The method for recycling waste zinc-manganese dioxide dry batteries and directly using the same for rechargeable zinc-manganese dioxide batteries according to claim 2, wherein the molar concentrations of the sulfuric acid and the hydrogen peroxide in the sulfuric acid-hydrogen peroxide solution in the step 1.2 are both 1-2 mol/L.
5. The method for recycling and directly using the waste zinc-manganese dry batteries for the rechargeable zinc-manganese batteries according to claim 1, wherein the pH value in the step 2 is adjusted to 3-5 for the first time and 1.5-2.5 for the second time.
6. The method for recycling waste zinc-manganese dry batteries and directly using the waste zinc-manganese dry batteries for rechargeable zinc-manganese batteries according to claim 1, wherein the heating concentration in the step 2 is carried out at a temperature of 70-90 ℃ for a period of 5-7 hours.
7. The method for recovering and directly using the waste zinc-manganese dioxide dry batteries as rechargeable zinc-manganese dioxide batteries according to claim 1, wherein the method further comprises the step of assembling the rechargeable zinc-manganese dioxide batteries by using the electrolyte solution obtained in step 2 as a working solution of the rechargeable zinc-manganese dioxide batteries and assisting positive and negative electrodes.
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